CN1049213C

CN1049213C - Process for producing p-toluenesulfonyl chloride

Info

Publication number: CN1049213C
Application number: CN97101400A
Authority: CN
Inventors: 刘国梁; 禾治宇; 冯彩英
Original assignee: Individual
Current assignee: Individual
Priority date: 1997-03-10
Filing date: 1997-03-10
Publication date: 2000-02-09
Anticipated expiration: 2017-03-10
Also published as: CN1163264A

Abstract

The present invention relates to a new method for producing p-toluenesulfonyl chloride, which takes toluene and chlorosulfonic acid as raw materials. The method comprises the procedures that the toluene and the chlorosulfonic acid react and generate a mixture; in order to sufficiently crystallize, stir speed is 2 to 50 rpm in a crystallizer, crystallization temperature is-10 to 30 DEG C, crystallization time is 1 to 8 hours, and the p-toluenesulfonyl chloride is obtained via direct filtration and water washing. The production method can shorten technical operation time, decrease energy consumption, obviously improve product quality and reduce raw material consumption, the concentration of waste sulfuric acid generated in production processes is more than 90%, and the waste sulfuric acid is convenient in use and process.

Description

A kind of method of making Tosyl chloride

The invention belongs to the manufacture method of organic fine Chemicals tosic acid chlorine.

The method of producing Tosyl chloride at present has several, method based on production ortho position body (o-toluenesulfonyl chloride) is wherein arranged, the contraposition body (Tosyl chloride) that this method generates is its byproduct, and the method based on production contraposition body is arranged, and its ortho isomer is its by product.And in the method based on the contraposition body, several diverse ways are arranged also.As German Patent Ger P 1172258, Ger p 1112978.The clear 56-46860 of U.S. Pat 3.686.300 Japan JP, wherein contraposition body yield the higher person surely belongs to the method for US3.686.300, this method has industrialized report (referring to Guoliang LIU China " Shanxi chemical industry ") 1,27,1990).The main process of this method is: toluene reacts in the presence of some salt with excessive chlorsulfonic acid, and the mixture that reaction obtains drips at leisure in frozen water, makes the reaction of excessive chlorsulfonic acid and water generate sulfuric acid and emit a large amount of heat.In the isolated like this Tosyl chloride, still be mingled with impurity such as ortho position body, obtain final product after further separating, the weak point of this method is, be mingled with more impurity impurity in the product, the color and luster outward appearance is relatively poor, has a negative impact for industrial uses such as pharmacy.It is many that the consumption of raw material chlorsulfonic acid still shows, and the sulfur waste acid that produces in the production is too rare, is unfavorable for industrial utilization and improvement, and chilling requirement is more during hydrolysis, consumes a large amount of electric energy.

The objective of the invention is at deficiency of the prior art, a kind of method of making Tosyl chloride is provided.At first make toluene with the purpose product in the chlorsulfonic acid post reaction mixture under certain conditions sufficient crystallising come out, and crystalline particle is increased.Employing does not add hydrolysis but the method for direct filtration is separated contraposition chlorine from mixture, most by product and impure impurity is stayed in the solution as far as possible, thereby the purity of product and color and luster are greatly improved.The consumption of chlorsulfonic acid is reduced in the least.The present invention also is for obtaining a kind of sulfur waste acid that contains a certain amount of unreacted chlorsulfonic acid, when making reaction the chlorsulfonic acid of inevitable excessive existence be not destroyed and have utilized again may.Can obtain simultaneously the vitriol oil more than 90%, this also provides convenience for give up vitriolic utilization and improvement.

Purpose of the present invention can reach by following measure: with industrial toluene and chlorsulfonic acid is raw material, in the presence of basic metal, alkaline-earth metal or ammonium salt, reacts in a reactor, and the hydrogenchloride that reaction generates is derived.Obtain a kind of mixture after the reaction, make the crystallization of purpose product complete through a crystallisation process, with filtering method crystallization is told then, further washing and separating isomerism thing make and obtain the higher contraposition chlorine products of purity again.Available reaction equation is expressed as:

Order of addition(of ingredients) is during reaction: import earlier required half the chlorsulfonic acid of reaction in reactor, add a kind of salt, 60～100 ℃ of control reaction temperature, be added dropwise to toluene, make reaction mass be cooled to 10～40 ℃ and add second half chlorsulfonic acid, reacted again 1～4 hour, the mol ratio of reaction mass be toluene than chlorsulfonic acid 1: 2～4, the mol ratio that adds salt is that toluene is 1: 0.3～0.7 than salt.After reaction finishes, for making contraposition body sufficient crystallising and increase crystalline particle, be sufficient crystallising in 2～50 rev/mins the crystallizer in stir speed (S.S.), its Tc is-10～30 ℃, and crystallization time is 1～8 hour; Carry out direct filtration behind the sufficient crystallising, filter cake is told isomer through washing, can obtain purity and be 95%, moisture about 4% Tosyl chloride and the 90% above vitriol oil.

Advantage of the present invention:

1, quality product obviously improves, and raw material consumption decreases.Because by product that reaction generates and foreign pigment big portion when filtering stays that sulfur waste acid is female to converge, thereby the higher color and luster of purpose product purity becomes white and since almost all solid phases from mixture, separate out equilibrated and move product yield is increased.

2, because the separation of reaction mixture is not the method that adopts hydrolysis in frozen water, the lock out operation when producing is speeded up, there are not a large amount of hydrolysis heat release simultaneously, reduce cold consumption during separation, reach purpose of energy saving.Owing to there is not the participation of water when separating, make the byproduct sulfuric acid concentration very high, can reach more than 90%.

3, owing to the needs of reaction, this law also needs more excessive chlorsulfonic acid, and after the employing dry method was separated, excessive unreacted chlorsulfonic acid was still stayed in the mother liquor spent acid, and this is just for utilizing this part chlorsulfonic acid that condition is provided again.

Be described in further detail below by embodiment:

In one 2000 liters reactor, agitator is housed, dropping funnel, temperature is taken into account the gas exporter, derive the water absorption unit of gas, add 7.5 moles of chlorsulfonic acids in the flask earlier, be heated to about 50 ℃ under stirring, add 2 moles of ammonium chlorides aly, make reaction content be warming up to 79～86 ℃ then, the toluene of Dropwise 5 mole, be cooled to 35～40 ℃ after dripping off, add second half chlorsulfonic acid, continue reaction 1 hour, reduce temperature to 20～25 of content again and ℃ placed 2 hours, the crystallization of contraposition this moment chlorine is almost all separated out, this crystallization filtration is told, ortho isomer is told in washing again, promptly get the finished product Tosyl chloride, content is more than 95%, about 65 ℃ of moisture about 4.0% fusing points, yield (in toluene) 78%, the total recovery that comprises the ortho position body is 86～87%.

Claims

1, a kind of method of making Tosyl chloride, in reactor, import earlier required half the chlorsulfonic acid of reaction, add 60～100 ℃ of a kind of salt control reaction temperature, be added dropwise to toluene, make reaction mass be cooled to 10～40 ℃ and add second half chlorsulfonic acid, reacted again 1～4 hour; The mol ratio of reaction mass is that toluene is 1: 2～4 than chlorsulfonic acid, and toluene is 1: 0.3～0.7 than salt; It is characterized in that: reaction finishes the back for making contraposition body sufficient crystallising and increase crystalline particle, is sufficient crystallising in 2～50 rev/mins the crystallizer in stir speed (S.S.), and its Tc is-10～30 ℃, and crystallization time is 1～8 hour; Can obtain the vitriol oil more than Tosyl chloride and 90% through direct filtration, washing again behind the sufficient crystallising.